Dyeing vinyl polymers



Patented June 13, 1944 DYEING VINYL POLYMERS Karl Heymann, Meadville, Pa., assignor to American Viscose Corporation, Wilmington, Del a corporation of Delaware No Drawing. Application March 7, 1940, Serial No. 322,844

16 Claims.

This invention relates to improvements in methods of dyeing yarns and other shapes comprising materials that are not readily permeable to water. More particularly, the invention relates to improvements in methods of dyeing yarns and other shapes comprising vinyl polymers, such as polymers of vinyl chloride and copolymers of vinyl acetate and vinyl chloride.

This application is a continuation in part of my application Serial Number 311,109, filed December 2'7, 1939.

Materials that are not readily permeable to water can not be satisfactorily dyed by the ordinary dyeing procedure used in dyeing cotton, wool, natural silk and regenerated cellulose. When ordinary methods of dyeing are attempted the dye either does not penetrate the material and no dyeing is effected Or when dyeing is efiected the color is not fast and leaches out.

Yarns and other shapes of cellulose acetate which are not readily permeable to water have been dyed when treated with a liquid swelling agent, such as alcohol, acetone or acetic acid. The swelling agent forms or opens pores in the material into which the dye penetrates. There are certain objections to the use of liquid swelling agents. Generally a large amount of swelling agent is required. Also the swelling agent has a tendency to weaken the yarn or shape.

I have discovered that yarns and other shapes comprising vinyl polymers, such as polymers of vinyl chloride and copolymers of vinyl acetate and vinyl chloride can be successfully dyed with suspension dyestuffs when the dyeing operation is carried out in the presence of suspensions of certain normally solid organic compounds which have a solubility in polymers of vinyl chloride and copolymers of vinyl acetate and vinyl chloride of 2% or greater under the conditions at which the dyeing is carried out. By the term suspension dyestuffs is meant dyestufis of the type applicable to cellulose acetate from a dispersion (insoluble anthraquinone and azo dyes) sometimes referred to as dispersal dyes, and the dyestufis referred to hereinafter in the examples by their trade names, are of this type. The compounds which are referred to as assistants inc ude:

Diphenyl Naphthalene Phenanthrene a-Naphthol b-Naphthol Thio-b-naphthol 2,4-dichloro-a-naphthol 2,4-dibromoa -naphthol o-Hydroxydiphenyl 2 chloro o phenylphenol 4 chloro o phenylphenol o-Cyclohexylphenol p-Chlorothymol 2,4-dichloroaniline 2,5-dichloroaniline a-Naphthylamine b-Naphthylamine Phenyl a-naphthylamine Phenyl b naphthylamine o-Aminodiphenyl p-Aminodiphenyl N,N diphenyl ethyl carbamate b-Naphthonitrile p-Chlorobenzaldehyde 2,4 dimethoxybenzaldehyde p-Dimethylaminobenzaldehyde 0 Hydroxyacetophenone Benzophenone p Hydroxybenzophenone Methyl-bnaphthylketone Camphor Benzalacetone Anisalacetone Benzoylacetone In carrying out my improved method of dye Benzalacetophenone l-hydroxy 2 acetonaphthone p Methoxybenzophenone Benzil Diphenyltriketone Dibenzoylmethane Desoxybenzoin Fluorenone 8-hydroxyquinoline Dibenzyl succinate Methyl p-bromoben zoate Diphenyl phthalate b-Naphthyl acetate Phenyl glycine ethylester Diphenyl carbonate Di-o-cresyl carbonate 2,4,6 tribromophenyl acetate a-Naphthyl acetate o-Diphenyl acetate Ethylene dibenzoate Glycerol tribenzoate Dicyclohexyl phthalate Dibenzyl phthalate Phenyl benzoate m-Cresyl benzoate p-Cresyl benzoate Benzhydrol Phenylbenzylcarbinol Fluorenyl alcohol b,b'-Diphenoxydiethyl ether p-Methoxydiphenyl Benzyl a naphthylether b Naphthylmethyiether p Methoxybenzopheing a suspension of a single assistant or several assistants together may be used. The assistant 2 aseam is. for example, dissolved in a suitable solvent. such as alcohol, and the assistant in solution and a suitable dispersing agent, such as that known in the trade as Igepon T. are added to the dyebath. The dye bath contains a suspension dyestufl. The assistant is precipitated in the dye bath in colloidal or very finely divided form. When amino compounds are used as assistants they may be dissolved in an acid solution and precipitated and dispersed in an alkaline dye bath. Phenols may be dissolved in an alkaline solution and precipitated and dispersed in an acid dye bath. Satisfactory results are also obtained under certain conditions when the phenol solution is added to the dye bath and is not dispersed. The yarn or shape to be dyed is treated with the dye bath containing the assistant in the ordinary manner. This procedure may be followed using various quantities of dyestufl and assistants with difl'erent dye bath ratios and temperatures of the dye baths depending upon the character of the material being dyed and the type of dyeing that is being carried out. A satisfactory procedure is one in which the dye bath ratio is 1:30 and contains 1.5% suspension dyestuff with or less of assistant based on the weight of the yarn or shape to be dyed. A suitable dye bath temperature is about 50" C. and the duration of the dyeing operation one hour. Other temperatures may also be used.

My invention may also be carried out by applying the assistant from suspension directly to the yarn or shape. When the yarn or shape is thereafter immersedin the dye bath the assistant aids the action of the dye bath on the yarn or shape in the same manner as when it has been added to the dye bath.

Instead of using either of the above methods, I may add the assistant directly to the vinyl polymers before the yarn or shape is formed. The yarn or shape containing the assistant is treated with the dye bath in the ordinary manner.

The following examples are illustrative of the invention:

Example 1.-Yarns comprising oopolymers of vinyl acetate and vinyl chloride were dyed in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestufl and 5% bnaphtnol based on the weight of the yarn. The temperatures of the dye baths were 60 C. and the duration of the dying operation one hour. The dyestuiis that were used were Cibacete Orange 2R Cibacete Scarlet G Acele Violet B Acele Yellow 3G A dye bath was also used with Cibacete Scarlet G 1% and Acele Violet B 1% as the dyestuif.

Example 2.Yarns comprising copolymers of vinyl acetate and vinyl chloride were dyed in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestuif and 5% pdimethylamino-benzaldehyde based on the weight of the yarn. The temperatures of the dye baths were 60 c and the duration of the dyeing operation one hour. The dyestuffs that were used were Celliton Red Violet RR Phenacyl Navy Blue PV Phenacyl Red R Celutate Brill. Blue B Cibacete Rubine BS Artisil Direct Yellow 36? Example 3.-Yarns comprising copolymers of vinyl acetate and vinyl chloride weredyed in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestuti and 1.5% benzophenone based on the weight of the yarn. The temperatures of the dye baths were 60% C. and the duration of the dyeing operation one hour. The dyestuil's that were used were Celliton Fast Pink BA Acele Scarlet G Calconese Orange 31w Cibacete Violet B Celutate Fast Blue GL Artisil Direct Yellow 36 ex. Phenacyl Red R Example 4.Yarns comprising copolymers of vinyl acetate and vinyl chloride were dye'd in dye baths having a dye bath ratio of 1:30 and containing 1.5% suspension dyestuii and 5% ohydroxydiphenyl based on the weight of the yarn. The temperatures or the dye baths were 60 C. and the duration of the dyeing operation one hour. The dyestuffs that were used were Celliton Pink RF Celliton Red BP Celliton Orange 3RN Cibacete Yellow 2RN Celliton Fast Yellow GRA Cibacete Yellow 5G Cibacete Brill. Blue BGG Celliton Fast Blue FFRS Celliton'Discharge Violet B Cibacete Discharge Violet 5R Camacyl Brill. Green B Phenacyl Red R Cibacete Violet B Artisil Direct Yellow 3GP ex. conc. Celliton Fast Brown 58A Camacyl Brill. Green B Phenacyl Red R Cibacete Violet B Artisil Direct Yellow 36? ex. cone. Celliton Fast Brown 5RA While preferred assistants and procedures have been shown it is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

What I claim is:

l. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestufl', in the presence of an organic compound selected from the group consisting of p-chlorobenzaldehyde, 2,4-dimethoxybenzaldehyde and p-dimethylaminobenzaldehyde.

2. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride. comprising the step of treating thuyarn or shape with a dye bath containing a suspension dyestufi, in the presence of an organic compound selected from the group consisting of p-chlorobenzaldehyde, 2,4-dimethoxybenzaldehyde and p-dimethylaminobenzaldehyde.

3. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuff and an organic compound selected from the group consisting of p chlorobenzaldehyde, 2,4 dimethcxybenzaldehyde and p-dimethylaminobenzaldehyde dispersed in the dye bath.

4. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuff and an organic compound selected from the group consisting of p-chlorobenzaldehyde, 2,4 dimethoxybenzaldehyde and p dimethylaminobenzaldehyde dispersed in the dye bath.

5. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestufi inthe presence of p-chlorobenzaldehyde.

6. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuif in the presence of 2,4-dimethoxybenzaldehyde.

'7. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuif in the presence of p-dimethylaminobenzaldehyde.

8. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuflf in the presence of p-chlorobenzaldehyde.

9. A method of dyeing yarns and other shapes comprising coplymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestufi in the presence of 2,4-dimethoxybenzaldehyde.

10. A method of dyeing yarns and other shapes I of treating the yarn or shape with a dye bath containing a suspension dyestufl and 2,4-dimethoxybenzaldehyde.

13. A method of dyeing yarns and other shapes comprising vinyl polymers, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuff and p-dimethylaminobenzaldehyde dispersed in the dye bath.

14. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuif and p-chlorobenzaldehyde dispersed in the dye bath.

15. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and. vinyl chloride, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuff and 2,4-dimethoxybenzaldehyde.

16. A method of dyeing yarns and other shapes comprising copolymers of vinyl acetate and vinyl chloride, comprising the step of treating the yarn or shape with a dye bath containing a suspension dyestuff and p-dimethylaminobenzaldehyde dispersed in the dye bath.

KARL HEYMANN. 

